Preparation of monochloroacetoacetamides



United States Patent 3,458,573 PREPARATION OF MONOCHLORO- ACETOACETAMIDES Charles H. Tieman, Modesto, Calif., assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed July 19, 1967, Ser. No. 654,325 Int. Cl. C07c 103/02 US. Cl. 260561 14 Claims ABSTRACT OF THE DISCLOSURE Preparation of N-alkyland N,N-dialkyl-Z-chloroacetoacetamides by reacting N-alkyland N,N-dialkylacetoacetamide with chloral, chlorinating the resultant chloral adduct, and dissociating the chlorinated chloral product.

Introduction N-alkyl and N,N-dialkyl-2-chloroacetoacetamides are intermediates in synthesizing an important class of insecticides comprising dialkyl phosphates of 3-hydroxycrotonic acids, as disclosed in the Whetstone and Stiles US. Patent No. 2,802,855. The patent teaches that the insecticides can be prepared by reacting the appropriate trialkyl phosphite with the appropriate N-alkyl or N,N-dialkyl-2- chloroacetoacetamides to form insecticides of the formula wherein R and R are among other things hydrogen or alkyl, and both R" substituents may be many organic radicals, including alkyl.

It is highly desirable that the above 2-chloroacetoacetamide reactants be substantially free of the 2,2-dichloroacetoacetamide analogs, as the latter amides will also react with the trialkyl phosphite to form the unwanted chlorinated products 0 CH Cl 0 R l o 'i N R"O R' wherein R", R and R are as described above.

These pollutants are highly undesirable as they are inferior insecticides and exhibit higher toxicity to mammals in comparison to the analogous unchlorinated compounds.

Consequently, it is of great importance to prepare a substantially pure 2-chloroacetoacetamide precursor free of the 2,2-dichloro analog.

The above 2-chloroacetoacetamides are customarily prepared by chlorination of the corresponding acetoacetamides. However, in the case of certain of these amides, for example, N-methylacetoacetamide, it has been found virtually impossible to prevent formation of substantial amounts of the corresponding 2,2-dichl0roacetoacetamides. For example, even by the most effective chlorination procedures known, 2-chloro-N-rnethylacetoacetamide can be produced in a purity of only about 80% to 85% with 15% to 20% of the 2,2-dichloro pollutant also being formed. Due to the close similarity of the physical properties of the monochloro and dichloro products, physical separation is not commercially feasible.

Therefore, discovery of a process for selectively preparing N-alkyland N,N-dialkyl-Z-chloroacetoacetamides substantially free of the 2,2-dichloro analog would be highly desirable.

3,458,573 Patented July 29, 1969 Statement of the invention The objects of the invention are accomplished in the preparation of N-alkyland N,N-dialkyl-Z-chloroacetoacetamides which comprises reacting N-alkylor N,N-dialkylacetoacetamide wherein the alkyl is up to 6 carbon atoms or hydrogen with chloral at elevated temperatures to form a chloral adduct of the formula 0 E. El) R CH -iil)C-N C13C-(]3OH \R' wherein R and R are hydrogen or alkyl of 1 to 6 carbon atoms. The chloral adduct is then reacted with a chlorinating agent containing active chlorine at a temperature of between about 0 C. and 70 C. to form a second chloral adduct of the formula wherein R and R are as described above.

The chlorinated chloral adduct is dissociated into chloral and N-alkylor N,N-dialkyl-2-chloroacetoacetamide simply by heating and separating the monochloroamide therefrom.

The process of the invention may be represented by the equation:

l Heat wherein R and R are as described above.

Process In order to facilitate full understanding of the invention, the process of the invention is set forth in more detail in the following description.

The process of the invention is conducted by reacting an N-alkylor N,N-dialkylacetoacetamide as described above with chloral, chlorinating the resultant chloral adduct, and then dissociating the chlorinated chloral adduct by heating and separating N-alkylor N,N-dialkyl- 2-chloroacetoacetamide therefrom.

The acetoacetamide starting materials have the structural formula wherein R and R may be hydrogen or alkyl of 1 to 6 carbon atoms. Examples of the amides wherein R is hydrogen or alkyl of l to 6 carbon atoms and R is hydrogen include acetoacetamide N-methylacetoacetamide N-propylacetoacetamide N-hexylacetoacetamide and the like.

Examples of the starting material wherein R and R are alkyl of 1 to 6 carbon atoms include N,N-dimethylacetoacetamide N-methyl-N-ethylacetoacetamide Nethyl-N-hexylacetoacetamide N-sec-butyl-N-pentylacetoacetamide N,N-dihexylacetoacetamide,

and the like.

Some of the starting amides such as N-methylacetoacetamide are available commercially, and all of the above acetoacetamides may be synthesized by methods known in the art. For example, the Whetstore and Stiles Patent US. 2,802,855, issued Aug. 13, 1957, and the references therein teach a method for synthesis of the above acetoacetamides.

The chloral, which is available commercially, is re acted with the N-alkyl or N,N-dia1kylacetoacetamide in an organic solvent which is inert under the reaction conditions, and in which the reactants are soluble enough to permit the reaction to proceed smoothly. The low solubility of the chloral adduct product in most solvents forces the reaction to completion by crystallizing out of the reaction medium as it is formed. However, a solvent which permits the reaction to proceed and in which the chloral adduct product is slightly soluble is also desirable as the subsequent chlorination step may then be carried out in the same reaction mixture.

Preferred solvents for the above chloral condensation and throughout the process are aromatic or aliphatic liquid hydrocarbons or halohydrocarbons which have a high boiling temperature. Examples of these solvents include carbon tetrachloride, 1,1,l-trichloroethane, chlorobenzene, chloroform, 1,1,2-trich1oroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, 1,2-dichloropropane, 1,4-dichlorobutane, methylcyclohexane, hexane, and their brominated analogs.

The chloral may be reacted with the acetoacetamide in a neutral solution or with the presence of an acid or base catalyst. The preferred catalysts are weak bases such as alkali metal salts and alkali earth metal salts of weak organic and inorganic acids such as potassium and sodium acetate and carbonate, dipotassium phosphate, borax, and sodium bicarbonate; ammonium salts of weak acids such as ammonium bicarbonate; and weak bases such as pyridine, and N,N-dimethylaniline. Such catalysts are used in concentrations of about 0.5 and 10 mole percent based on the moles of acetoacetamide starting material used. Especially preferred is a concentration of about 2 mole percent.

The presence of a mild base in the reaction medium appears to accelerate the chloral condensation reaction by at least a factor of 10. Suitable mild bases are the alkali metal and .alkaline earth metal carbonates and acetates. Preferred among these bases are sodium carbonates and sodium acetate. The bases may be used in amounts of between about 0.005 to 0.1 molar based on the acetoacetamide starting material with about a 0.02 molar amount being preferred.

The solvent should be an anhydrous as possible since chloral will readily react with water, resulting in a net loss of chloral available for the condensation with the acetoacetamide. To avoid excessive losses of the chloral, water should not be present in the reaction mixtures in quantities greater than 5% by weight. Consequently, a slight molar excess of chloral may be advantageous in the condensation reaction.

The chloral condensation reaction may be carried out at subatmospheric, atmospheric pressures, or superatmospheric pressure, although atmospheric pressure is preferred. Temperatures of between about 0 C. to C. are operable in the condensation reaction, although higher or lower temperatures may be used if advantageous. The preferred temperature range is between about 25 C. to 70 C.

The resulting chloral adduct solution may be directly chlorinated without any preliminary purification steps, or the adduct may be purified and then chlorinated. In the case where the reaction mixture is directly chlorinated the preferred solvents throughout the process are 1,2- dichloropropane, 1,1,2-trichloroethane and carbon tetrachloride.

When the chloral adduct product is purified before chlorination, any of the solvents discussed as useful in the condensation reaction are about equally useful. The purification may be carried out by procedures standard in the art such as crystallization, extraction, evaporation, or distillation of excess solvent and chloral, etc.

The resultant chloral adduct is chlorinated with a chlorinating agent in liquid phase at a temperature between about 0 C. to 70 C. to form the chlorinated chloral adduct. The reaction may be carried out at subatmospheric, atmospheric or superatmospheric pressure. The chlorination is generally mildly exothermic and is preferably carried out at a temperature between about 0 C. to 70 C. with a temperature of between about 15 C. and 35 C. being most preferred. Higher temperatures than the above-described should be avoided because reversion of the chloral adduct to the acetoacetamide and chloral may result. This would lead to over chlorination of the starting material which would yield the undesirable 2,2-dichloroacetoacetamide.

The solvents useful in the chlorination reaction are the same as those useful in the preceding condensation reaction. As explained above, the same reaction medium may be used for both the condensation and the chlorination reactions. Therefore, the above discussion of solvents for the condensation reaction is equally applicable for the chlorination reaction.

The suitable chlorinating agents for the above reaction are those compounds containing active chlorine, which is meant to define compounds which provide or are considered to provide chlorine in the cationic form as the chlorinium ion, Cl+. Generally, these compounds are those in which chlorine is attached directly to an eleclronegative nitrogen, oxygen or sulfur atom.

Examples of these chlorinating agents include C1 N- chloramide (monochlorammonia), N-chloro primary and secondary amines of the structure wherein each R is hydrogen or an alkyl group of 1 to carbon .atoms of either straight chain or branched chain configuration such as N-chloro-N-methylamine, N-chloro-N,N-dibutylarnine, N-chloro-N-pentyl N sec-butylamine, N-chloro-N,N-didecylamine, and the like.

Also included are the N-chloroacetamides of the structure OR III wherein X is chlorine, M is 1 or 2, m-I-n is 2, and R and R" each may be hydrogen, an alkyl group of up to 10 carbon atoms, a phenyl unsubstituted or substituted by one or more of chlorine, nitro, cyano, and alkoxy wherein each alkyl group contains from 1 to 10 carbon atoms, and phenylalkyl wherein each alkyl group contains from 1 to 6 carbon atoms, or R is of the structure wherein X is chlorine, p is 0, 1 or 2, and p+q is 2, and R is an alkyl containing from 1 to 10 carbon atoms as in the ureas, such as N-chlorourea, N,N-dichlorurea, N-methyl-N'-chlorourea and the like; or R is of the structure wherein R'' is an alkyl of up to 10 carbon atoms as in the urethanes, for example, methyl-N-chlorourethane, ethyl-N-methyl-N-chlorourethane, propyl N-methyl-N- chlorourethane, and the like.

Still further examples include hypochlorous acid and alkyl esters thereof wherein the alkyl contains from 1 to 20 carbon atoms; the mono-, di-, and trichloroisocyanurates of U.S. Patents Nos. 3,035,056 and 3,035,057; N,N dichloro azo dicarbodiamidine, benzendiazonium perchloride, pyridine dichloride, N-substituted biguanides of U.S. Patent No. 2,945,061, sulfuryl chloride, sulfoxamides, sulfonamides, such as chloramine B and chloramine T, and N-chlorooxamides.

The above examples of chlorinating agents containing active chlorine are either commercially available such as chloramine T, or are readily prepared by methods known to the art, for example in the above-identified patents.

The preferred chlorinating agents are the N-chloro primary and secondary amines, the N-chloro-amides and imides, the N-chloro ureas, and sulfuryl chloride. The chlorinating agent may be pre-formed and added to the reaction mixture as is the case with sulfuryl chloride, or may be formed just before the reaction or may be formed in situ in the reaction mixture as in the case with the N- chlorourea.

The chlorinating agent should be present in the reaction or added during the reaction in equimolar amounts with the acetoacetamide starting material. A slight molar excess of chlorinating agent may be used in order to insure complete chlorination of the chloral adduct. Use of less than equimolar amounts of the chlorinating agent should be avoided as this results in a corresponding reduction in the chloral adduct that is chlorinated.

The chlorination reaction is slightly exothermic. Therefore, to insure control of the reaction and to avoid excessive temperatures the chlorinating agent is added slowly during the reaction. Further control of the amount of heat given off by the reaction can be obtained by mixing the chlorinating agent with one of the above solvents. The rate of reaction appears to be benefited by rapid stirring of the reaction mixture since this allows the quick addition of the chlorinating agent 'by increasing contact of the chlorinating agent with the partially solubilized adduct.

Most of the chlorinated chloral adduct will crystallize out of the reaction solution in some solvents to the extent that only about 10% of the chlorinated product will remain in solution. Since the chlorinated chloral .adduct will not react with active chlorine compounds under the chlorination reaction conditions, the precipitate may be filtered out of the solution, and the mother liquor may be reused as the solvent in the chlorination reaction.

The chlorinated chloral adduct is then dissociated to the Z-chloroacetoacetamide and chloral by subjecting it to temperatures of about 15 C. to 200 C. and the 2- chloroacetoacetarnide is separated out of the reaction mixture.

The dissociation reaction may be carried out in the same reaction mixture used for the condensation and chlorination reactions. This would result in a continuous one-pot process for the multi-step process of the invention for the synthesis of the 2-chloroacetoacetamides described above.

However, it may be more advantageous to run the condensation and chlorination reactions in the same solvent, filter off the resulting crystallized chlorinated chloral adduct, and dissociating the adduct separately. The separation procedure removes the pure chlorinated adduct from the reaction mixture which may contain impurities that will decrease the efliciency of the dissociation reaction process. For example, any excess sulfuryl chloride would be removed with the mother liquor Otherwise, any sulfuryl chloride present during the dissociation reaction would react with the desired 2-chloroacetoacetamide to form the unwanted 2-2-dichloroacetoacetamide.

The chlorinated chloral adduct may be dissociated by heating it above its melting point under vcauum. However, a cleaner product is obtained more rapidly by the use of a diluent. Suitable diluents are those solvents discussed above for the condensation reaction. The rate of dissociation increases with temperature, therefore, the higher boiling solvents are preferred. For example, the dissociation required 5 hours of reflux of the adduct in 1, 2-dichloroethane (boiling point 84 C.) whereas only 2 hours was needed with 1,2-dichloropropane as a solvent (96 C.) and only 0.5 hour of refluxing in 1,1,2-trichloroethane (boiling point 114 C.) completed the dissociation.

A convenient procedure for dissociating the adduct is to reflux the adduct with a solvent in a ratio of one part adduct by weight to two volumes solvent for a time sufficient for complete dissociation, which will depend on the particular solvent employed. The dissociation may be carried out in an essentially neutral solution; however, the rate of dissociation can be accelerated at least a hundredfold by the presence of weak bases such as those discussed above for the condensation reaction.

Further, the presence of weak bases allows the dissociation to be performed at lower temperatures. As in the condensation reaction, the amount of basic catalyst required varies from 0.005 molar to 0.1 molar based upon the moles of adduct being reacted.

An alternate procedure for the dissociation reaction is heating a slurry of the chlorinated chloral adduct in water to a temperature between about 10 C. to 50 C. in th presence of a weak base. The dissociation proceeds rapidly and is complete in several minutes. The desired 2-chloroacetoacetamide and chloral hydrate are the products of this method.

Once the dissociation is completed, the desired monochlorinated product is recovered from the reaction mixthe examples, the proportions are given in parts by weight unless otherwise noted.

EXAMPLE I A slurry of 23 g. (0.2 mole) of N-methylacetoacetature by methods well known to th art. For example, the mide and 31 111016) 9 freshly fiistilled al in reaction mixture may be cooled and h hl i d id 200 ml. of carbon tetrachlorlde was stirred and refluxed separated out by selective phase separation. Other methods for 3 hours and allowed to Stand Ovemlght at 10031 9 include azeotropic distillation of excess chloral with cycloperature. The solid product was filtered and washed with hexane, distillation in vacuo, crystallization and the like. flesh Solvent f glve 50 0f N- y -2-( y- 2-chloroacetoacetamid products of the process of the dfoxy-lzzz'llrlchlofoethyl)-acet0aetam1deinvention are f the structure Analysis for C H Cl NO Calculated: Cl, 40.6; N,

0 H 0 R 5.3.Found: Cl, 40.4; N, 5.2. H l EXAMPLE H 1 To a stirred slurry of 131 g. (0.5 mole) of N-methyl- 2 l hydroxy 2,2,2 trichloroethyl)-acetoacetamide Wherem R and R each may be hydrogm} or alkyl Pf 1 in 800 ml. of methylene chloride was added 74 g. (0.5 to 6 carbon atoms. Examples of the amides whereln R h d 0 or alk 1 of 1 to 6 carbon atoms and is mole) of sulfuryl chloride over a period of about 0.25 L I p 1 d S y hour at After being stirred for another 2.5 hours y rogen me u e at 25 the slurry was cooled to 5 and was filtered to give 2-chloroacetoacetamide 130 g. (88%) of N-methyl 2 (l-hydroxy-2,2,2-trichlo- N-mcthyl-Z-chloroacetoacetamide roethyl)-2-chloroacetoacetamide. N-butyl-2chloroacetoacetamide Analysis for C H Cl N0 Calculated: Cl, 47.8; N, 4.7. N-n-propyl-Z-chloroacetoacetamide 25 Found: Cl, 47.8; N, 4.5. N-hexyl-2-chloroacetoacetamide EXAMPLE HI and the like.

Examples of the product wherein R and R' are alkyl A mixture of 31 g. (0.21 mole) of freshly dlstilled of 1 to 6 carbon atoms include chloral and 23 g. (0.2 mole) of N-methylacetoacetamide in 200 ml. of carbon tetrachloride was stirred and re- N,N-dlm6thyl'z'chloroacetoacetamlde fluxed for 2.5 hours. The mixture was allowed to stand N, yl-N- y q overnight at room temperature and, after dilution with -P{PY -P l f 100 ml. of carbon tetrachloride, was treated with 30 g. Y (0.22 mole) of sulfuryl chloride at 25. The slurry was and the like 5 stirred for 2 hours, was cooled to 10 and was filtered to As N-methyl-Z-chloroacetoacetamide is the preferred glve chlorinated-0111031 adduct- A product of this Process, the f ll i examples will be solut1on of th1s solid in 100 ml. of l,l,2-tr1chloroethane discussed in terms of N-methylacetoacetamide as a startwas mfluxed for one f The sPlutlon was decanted ing material and 211101.o N methylacetoacetamide as the from a small amount of insoluble 011 and was evaporated, Product of the invention 40 finally at 80 (0.3 mm.), to leave 28 g. (93%) of tan The examples demonstrat that the process of the in- Sohd, a s thaln chloral by gas chromatog' vention produced 2 chloro NmethYlacetoacetamide in raphy. Iodide titration indicated the presence of 94.7% crude yields in excess of 90% with a purity of up to 95% N'methyl'z'chloroacetoaceta'mdeand free of any undesirable 2,Z-dichloroacetoacetamide. EXAMPLE This high purity and high yield of N-chloromethylaceto- IV acetamide and the absence of unwanted impurities make Following the procedure outlined in Exampl eI, several the process of the invention highly desirable for the runs were made illustrating Step 1 of the invention, i.e., synthesis of 2-chloro-N-methylacetoacetamide for used as the condensation of chloral with the acetoacetamide. In an intermediate in the above described synthesis of phoseach run, the amide was N-methylacetoacetamide. The phate insecticides. various solvents, times and temperatures employed, as The novel and useful features of the process of the well as the yields and chlorine analyses, are given in invention are illustrated by the following examples. In Table I. Calculated analysis for chlorine is 40.6%.

TABLE I Anal. Amide, Chloral, Vol. Time, Temp, Yield, percent moles moles Solvent ml hours 0. percent 0.0 0.04 01101,, 000 0 05 74 30.0 0.3 0.31 01101 100 #0 05 40.5 0.20 0. 31 011013 100 0.5 05 31 40.0 1.0 1. 05 01101; 350 2 05 84 40.5 0.20 0. 35 001. 200 B 1 7s 03 30.0 1.0 1.18 001 700 2.5 78 03 30.0 0.2 0.21 0011 200 3 7s 01 30.0 0.2 0. 21 0014 200 2.5 78 05 40.4 0.2 0.204 011,6101101, 50 0.5 70 85 0.2 0.204 01110101101, 50 7.5 70 as 40.3 0.2 0.204 0,111,011, 200 5 70 05 38.8 1.0 1.05 0.11.01 500 5 70 78 40.5 1.1 0.105 011 01101015501 30 0) 25 01 40.3

1 Molecular weight= 115.

2 Molecular weight=147.5 (commercial grade employed, unless otherwise noted). 3 Yield base on weight of solid crystallizing from reaction mixture.

4 Redistilled from commercial grade material.

5 Letstand overnight at room temperature after heating.

0 Sodium carbonate (0.07 mole) added as catalyst.

* 4 days.

9 EXAMPLE v Following the procedure outlined in Example II, sevperature between about C. to 70 C. to form a second chloral adduct of the formula eral runs were made using sulfuryl chloride as a chlori- 0 O1 0 R nating agent for the chlorination of N-methyl-Zfl-hydroxy-2,2,2 trichloroethyl)-acetoacetamide, the chloral 5 1 adduct of Step 1 of the invention. The results and reac- C1C OH R tion conditions are given below in Table II. H

TABLE II wherein R and R are as described above; and

Anal 3 (3) dissociating the chlorinated chloral adduct by heat- Adduct, SOzCh, Yieldfl percent ing the adduct to a temperature between about C.

mfles mles S01v6 percent 1 to 200 C. and separating therefrom a monochloro- 0.18 0.18 0112012 500 75 47.8 acetoacetamide of the formula 0.15 0.15 0112012 250 82 0.25 0.25 CHzClg 300 82 0 C1 0 R 0.5 0.5 0112014 800 88 47.8 g I It 0.5 0.55 CHzClz 1,500 75 45.3 15 CH3- N 0.35 0. 37 011.012 550 03 46.8 I 0. 27 0.27 C014 000 00 45.3 H R 1 lflolecularvveight=262i wherein R and R are as described above.

9 Yield based on weight of solid filtered from reaction mixture; product was N-methyl-Z-(l hydroxy-2,2,2-triehloroethyl)-2-chloroacetoacetamide, The PrPCeSS of claim} Wherem i acetoacetamlde molecmar weight=297 is reacted with chloral 1n l1qu1d phase 1n the presence of i galculatged analgsis 1i011; chllolrinfi is 47.8%. a k base.

re are 111091! 011 e THC On 9.

p 3. The process of claim 1 wherein the acetoacetamlde is reacted with chloral in liquid phase in the presence of EXAMPLE VI a weak base selected from the group of sodium carbonate Following the procedure of Examples I, II and III, a and sodlum acetate. number of runs were made to illustrate the conversion 4- The p ocess 0f Claim 2 Wh Iem the base is present of N-methylacetoacetamide with all three steps of the In an amount between about 0.005 and 0.1 molar based invention combined. Reaction conditions and results are on the moles of the amide being reacted. given in Table III. 5. The process of claim 1 wherein the chloral adduct TABLE III Content of Chlorination Dissociation Yield MMCAAE Crude in Crude MMAA, Chloral, Time, Temp, $02011, V01. V01. MMCAA Product, moles moles Solvent Vol. (ml.) hours C. moles Solvent (1111.) Solvent (ml) (4) percent 6 0.1 0.105 C014 6 40-50 0.1 Same+ 40 Same+TCE 102 844 0.2 0. 21 001 200 2.5 78 0.19 TOE 100 Same 97 91 0.2 0.21 C014 200 2.5 78 0. 22 Same+ 100 TOE 100 93 95 0.2 0. 21 C014 200 3 7s 0. 22 Same TOE 100 94 93 0.2 0. 21 001., 200 3 7s 0. 22 Same TOE 100 0.2 0. 21 C014 200 1 78 0.22 Same TOE 100 0.2 0. 21 001.. 200 3 78 0.22 Same 'ICE 0.2 0. 21 C014 200 3 78 0.18 TOE 100 Same 0.2 0. 21 C014 200 3 78 0. 22 0014 200 TOE 0.2 0.204 T015 50 0.5 50 0.22 Same TCE 0.1 0.15 TOE 20 2 90 0.1 Same Same 0.1 0.2 'ICE 30 2 90 0.1 Same Same 0.1 0.105 TOE 30 0 50 0.1 Same Same 0.2 0. 204 0.11.01 100 3.5 70-80 0. 22 Same 0 11.01 0.2 0. 21 0 11 200 B 3 70 0. 22 Same 'ICE 0.1 0.11 CO1; 00 TUE 94 92 0.1 0.1 TOE 45 Same 100 95 Molecular weight=115; MMAA=monornethylaeetoaeetamide (N- By iodide titration. methylacetoacetamide). 7 Not redistilled.

2 Redistilled (molecular weight=147.5). 8 Also, overnight at room temperature.

3 Heated at 110 C. for 1-2 hours. TCE=l,l,2trichloroethane. Overall yield of 88%.

4 Weight yield, stripped to 80 C. (0.5mm.pressu.re);molecu.lar weight= Crude product mostly N-methyl-Z-(l-hydroxy-2,2,2-trichloroethyl)- 149.5. 2-chl0roacetoacetamide.

5 MMCAA=n1onomethylchloroacetoacetamide (N-methyl-Z-chloro- 11 N-rnethyl-2-(-1-hydroxy-2,2,2-trichloroethy1) -acetoacetamlde preacetoacetamide). pared in chloroform.

We claim as our invention:

1. A process comprising least an equimolar amount of a chlorinating agent (1) reacting an amide of the formula containing active chlorine in liquid phase at a tem- O O R and chlorinating agent are reacted at a temperature of II II between about 15 C. and 35 C. CH3- CH:CN

6. The process of claim 1 wherein the chlorinated chloral adduct is dissociated in liquid phase in the presence of a weak base. wherein R and R are elected from the group con. 7- The process of claim 6 wherein the dissociation in i ti of h d d lk l of 1 to 6 carbon atoms, liquid phase is carried out in the presence of a weak base with chloral at a temperature between about 0l25 selected from the group of sodium blcarbonate and so- C. in liquid phase in the presence of an anhydrous dium acetate. solvent o form a c l adduct of e fOImIIIa 8. The process of claim 7 wherein the base is present in O H O R an amount between about 0.005 and 0.1 molar based on lLJA the moles of the adduct being dissociated.

C I OH 9. The process of claim 1 wherein the dissociation re- 1 action is carried out by heating the chlorinated chloral H adduct above its melting point under vacuum.

10. The process of claim 1 wherein the dissociation is h i R d R are as d ib b carried out at a temperature of between about 50 C. and (2) reacting the chloral adduct with a mixture of at C.

11 11. The process of claim 1 wherein the chlorinating agent is sulfuryl chloride.

12. The process of claim 1 wherein the chlorinating agent is C1 13. The process of claim 1 wherein the final product is 5 N-methyl-2-chloroacetoacetamide.

14. The process of claim 1 wherein the final product is N,N-dimethyl-2-chloroacetoacetarnide.

References Cited UNITED STATES PATENTS 3,284,500 11/1966 Tiernan 26O561 ALEX MAZEL, Primary Examiner J. A. NARCAVAGE, Assistant Examiner 

